The archdiocese, having been founded in 1595 in Nueva Cáceres (now Naga City), is also considered one of the oldest dioceses in the Philippines with Cebu, Segovia and Manila, and once had jurisdiction that stretched from Samar in the south and Isabela Province in the north.

The Archdiocese of Nueva Caceres is also home to Our Lady of Peñafrancia, the patroness of the Bicol Region, and is considered to be one of the largest Marian pilgrimages in Asia.

It was elevated to the status of archdiocese on June 29, 1951 through the virtue of the papal bull "Quo in Philippine Republica" by Pope Pius XII.

[citation needed] Leonardo Legaspi, who was also the first Filipino Rector Magnificus of the Pontifical and Royal University of Santo Tomas, and the first vicar of the Dominican Province of the Philippines once served as archbishop of the archdiocese.

[citation needed] According to a Holy See Press Office Vatican Information Service (VIS) online news release on Saturday, September 8, 2012, Pope Benedict XVI had appointed Bishop Prelate of the Roman Catholic Territorial Prelature of Infanta Rolando J. Tria Tirona as Metropolitan Archbishop of the Roman Catholic Archdiocese of Cáceres to succeed the retiring Archbishop Legaspi.